Carbon-carbon composition, their preparation and use therefore as negative electrode for li-ion batteries

ABSTRACT

A composite of particles of Carbon#I-Cmlrbon#2, wherein Carbon# 1  means a low cristallinity cmbon and Cro#means a high ctistallinity carbon and the use of these particles in electrochernca systems, in spoxi equipments, in foundry industry

TECHNICAL FIELD

The present invention relates to composite carbone-carbone particles obtained from a low cristallinity carbon and of a high cristallinity carbon.

The present invention also relates to a process for preparing the composite carbon-carbon particles of the invention by dispersing and mixing together low cristallinity carbon particles with high cristallinity carbon particles.

The present invention also relates to a process for preparing the composite carbone-carbone particles of the invention by mixing carbon particles with a polymeric substance and by heating the mixture thereby obtained until carbonization of the polymeric substance on the surface of the carbon particles.

A further aspect of the present invention is the use of the composite particles inter alia in foundry industry, in sports equipment, in the automobile and in aeronautic industries and the use of those particles as constituents of electrode material in electrochemical systems.

PRIOR ART

Li-ion batteries are now considered one of the best existing power sources for portable electronics such as cell-phones, camcorders, laptop computer and power tools. A Li-ion cell typically consists of a carbon-based negative electrode (NE) porous polymer membrane separator (polypropylene and/or polyethylene) and a lithium transition metal oxide (LiMO₂, M=Co, Ni, or Mn) based positive electrode as described in Nishi in Advances in Lithium-ion batteries edited by W. Schalkwijik Cluwer Academic/plenum publishers, 2002, page 233, electrodes are made by casting slurries of active materials, polymer-based binder (i.e. polyvinylidene difluoride, PVDF) and small amounts of high surface area carbon onto metal foil current collectors. Mixtures of Li-salts and organic solvents provide an electrolyte medium for Li-ions to shuttle between the PE and NE, During charge, Li-ions deintercalate from the PE and intercalate into the NE, while the reverse takes place during discharge as mentioned in A. Webber and G. Blomgren in Adavances in Lithium-ion batteries, edited by W. Schalkwijik Cluwer Academic/plenum publishers, 2002, on page 185.

The evolving products require a Li-ion cell with a longer cycle-life, higher energy and charge/discharge rate capabilities. Long cycle-life e.g. is critical for the Li-ion battery to last the lifetime of the host device (such as: embedded electronics and medical prosthesis); and high capacity and rate capability are needed for the EV, aerospace and military applications.

For the development of Li-ions of such unique properties, battery manufacturers and research groups have been investigating possible applications of new and/or modified PE and NE materials.

These included utilization of In/Si-based intermetallic alloys, metal-carbon and carbon-carbon composites as NE-materials, and mixed metal-oxides as PE-material, as disclosed in R. Huggins in Handbook of battery materials edited by J. Besenhard Wiley-veh, 1999, page 359.

However, despite their high capacity, available NE-materials containing carbon-carbon composite, present the drawback of limited cyclic life, when available NE-materials containing In/Si-based intermetallic alloys despite their capacity present the drawback to be used commercial lithium-ion batteries.

Electrodes are made by casting slurries of active materials, polymer-based binder (i.e. polyvinylidene difluoride, PVDF) and small amounts of high surface area carbon onto metal foil current collectors. Mixtures of Li-salts and organic solvents provide an electrolyte medium for Li-ions to shuttle between the PE and NE. During charge, Li-ions deintercalate from the PE and intercalate into the NE, while the reverse takes place during discharge.

The evolving products are demanding for Li-ion cells with longer cycle-life, higher energy and charge/discharge rate capabilities. Long cycle-life e.g. is critical if the Li-ion battery should last the lifetime of the host device (such as: embedded electronics and medical prosthesis); and high capacity and rate capability are needed for the EV, aerospace and military applications.

For the development of Li-ions of such unique properties, battery manufactures and research groups have investigating possible application of new and/or modified PE and NE materials, including the utilization of In/Si-based inter-metallic alloys, metal-carbon and carbon-carbon composites as NE-materials, and mixed metal-oxides as PE-material.

However, despite their high capacity, available NE-materials containing carbon-carbon composite present the drawback of cyclic life, when available NE-materials containing In/Si-based intermetallic alloys despite their capacity present the drawback to be used commercial lithium-ion batteries.

There was therefore a need for a positive electrode and/or negative electrode material free of the drawbacks usually associated with the corresponding prior art known materials and presenting inter alia at least one of the following properties: a long cycle life, a high capacity, a low self discharge, a good compatibility with a low volume expansion and with a low reactivity required for the safety of batteries.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph that represents the thermal profile of the heat treatment of a (Carbon#1: polymerized PF-matrix) prepared according to a process of the invention as described thereafter under “sample preparation”.

FIGS. 2 a to 2 d are schematic pictorial model representations of the steps occurring during processing of the proposed carbon-carbon composite material for NE in Li-ion cells, in the case wherein carbon#2 progressively covers carbon#1 particles with a network of carbon2.

FIG. 3A is an SEM image of the carbon-carbon material according to sample 1 hereinafter defined in Table I, the carbon#2 is derived from carbonization of PF, which cover partially the surface of carbon#1 (graphite).

FIG. 3B is the same SEM image as in FIG. 3A, but at a larger scale.

FIG. 4A is an SEM image of the carbon-carbon material according to sample 2 defined herein after in Table I, the carbon#2 is derived from carbonization of PF and covers almost totally the surface of carbon#1 (graphite); the measured particle size of carbon#2 is from 39 nm to 500 nm.

FIG. 4B is the same SEM image as in FIG. 4A, at a larger scale.

FIG. 5A is an SEM image of the carbon-carbon material according to sample 3 as defined hereinafter in Table I. The carbon#2 is derived from carbonization of PF, which covers partially the surface of carbon#1 (graphite), but still some graphite particles are not covered at all. The particle size of carbon#2 is from 20 nm to 500 nm.

FIG. 5B is the same image as in FIG. 5A but at a larger scale.

FIG. 6A is an SEM image of the carbon-carbon material according to sample 4 as defined hereinafter in Table I. The carbon#2 is derived from carbonization of PF, which covers almost totally the surface of carbon#1 (graphite). The carbon#2 is more compact and it's particle size is form 20 nm to 500 nm.

FIG. 6B is the same image as in FIG. 6A but at a larger scale.

FIG. 7 shows Transmission Electron Micrograph a carbon-carbon composite according to the invention, that has been prepared according to samples 3 and 4 and beat treated to 2,500° C.

DESCRIPTION OF THE INVENTION

A first object of the present invention is constituted by composite particles of carbon, thereafter named Carbon#1-Carbon#2 composite particles, wherein Carbon#1 means a low cristallinity carbon and Carbon#2 means a high cristallinity carbon.

In the framework of the present invention, the expression Carbon#1 means carbon particles, having a low cristallinity characterized by wide-angle X ray diffraction measurements, i.e by an average lattice constant d=(002) of 0.350 nm or more and a crystallite size L=(002) in the direction of C axis of 25 nm or less. Such low cristallinity carbon is more extensively described in Carbon electrochemical and physicochemical properties, John Wiley, New York, 1988.

According to a preferred embodiment of the invention low cristallinity carbons are selected in the group constituted by hard carbon, glassy carbons, polymer derived carbons and petroleum cokes.

In the framework of the present invention, the expression Carbon#2 means a high crystallinity carbon characterized by wide-angle X ray diffraction measurements, i.e by an average lattice constant d=(002) of 0.338 nm or less and a crystallinity size L=(002) in the direction of C axis of 40 nm or more. Such high crystallinity carbon is more extensively defined in Carbon electrochemical and physicochemicai properties, John Wiley, New York, 1988. According to a preferred embodiment of the invention such high cristallinity carbon is selected in the group constituted by graphite, preferably natural graphites, kish graphite, pyrolytic graphite, gas-growth graphite or any artificial graphite.

A preferred family of Carbon#1-Carbon#2 composite particles of the invention is constituted by those composite particles having at least one of the following physical properties:

-   -   a package density, according to the tap density method         associated to the apparatus commercialized under the name Logan         Instrument Corp. Model Tap-2, that is >0,5 g/cc.     -   a particle size, measured according to the SEM method associated         with apparatus Microtac model X100 Particle Analyser, ranges         from 0.5 to 100 micrometers; and     -   a specific surface area, measured according to the BET method,         ranging from 1 to 50 m²/g.

As shown inter alia in FIGS. 2, the composite particles of the invention may be described as low cristallinity particles of Carbon#1 embedded or surrounded by a matrix (or by a network) of graphite Carbon#2.

According to an another aspect of the invention, the composite particles of the invention may be described as particles of Carbon#2 embedded or surrounded by a matrix (or a network) of Carbon#1.

Therefore, particles of a high cristallinity carbon (preferably a graphitic carbon) are embedded within or surrounded by the matrix of a second carbon that has lower degree of cristallinity (graphitization), also known as hard carbon.

A second object of the present invention is constituted by the use of the composite particles according to the first object of the present invention as a constituent of an electrode material, preferably as a constituent of a N-E (negative electrode) material in electrochemical systems, in the foundry industry, in the car and in aeronautic industries, in sports equipment.

A third object of the present invention is constituted by negative electrodes comprising between 2 to 98% and preferably by those comprising at least 90 weight per cent of a composite particles of the invention, the remaining being preferably constituted by at least one binder. The binder is preferably of the PVDF type.

A fourth object of the present invention is constituted by a battery system comprising at least one electrode containing carbon-carbon composite particles according the invention. Preferably, in the battery system of the invention, the electrode containing composite particles is a negative electrode.

According to an another embodiment, the battery system is of the N-E/electrolyte/PE type.

According to a further preferred embodiment of the invention the battery system consists, of wined/stacked layers or of winded/stacked layers of electrodes of electrodes, at least one of said electrodes comprising carbon-carbon composite particles according to the invention.

A preferred embodiment is constituted by Li-ion battery comprising a negative electrode, a positive electrode and a porous polymer membrane separator for example of the Celguard type, wherein at least one of said electrodes is a negative electrode according to the invention.

A fifth object of the present invention is constituted by a process for preparing the composite material particles according to the first object of the invention. This process preferably comprises the steps of dispersing and mixing preferably by using ball milling, at least one Carbon#1 powder, preferably in the form of a slurry of a polymeric substance that results in carbon particles by heat treatment. The polymeric substances preferably a polymer with a high carbon content, is preferably dispersed in an organic solvent in a slurry that can easily stick on the surface of the carbon particles to be covered. The polymeric material is preferably dispersed in a liquid Phenolic Resin (PF). Appropriate phenolic resins are for example those commonly used in the foundry industry. Phenolic resins are the most widely used resin binders in the foundry industry. They are produced by polycondensation of phenols with formaldehyde. The three types of resins presented in the following Table differ in catalyst and mole ratio of reactants used in their preparation. Furthermore, they have different molecular structures and reactivities and require different curing agents. TABLE Some examples of Phenolic Resins Novolacs Resoles Polybenzylic ethers ratio of phenol to >1 <1 <1 formaldehyde acidic basic neutral, metal sal pH conditions thermoplastic thermosetting anhydrous thermal behavior shell process hot-box process thermosetting foundry process no-bake cold-box process process no-bake process

There are two further categories of epoxy resins that may be successfully used, namely the glycidyl epoxy, and non-glycidyl epoxy resins. The glycidyl epoxies are further classified as glycidyl-ether, glycidyl-ester and glycidyl-amine.

The diglycidyl ether of bisphenol-A (DGEBA) is a typical commercial epoxy resin and is synthesised by reacting bisphenol-A with epichlorobydrin in presence of a basic catalyst.

The Novolac Epoxy Resins are glycidyl ethers of phlenolic novolac resins.

The mixing process is advantageously continued until complete dispersion of Carbon#1 in the PF and preferably until vaporization of 40 to 60 wt % of the containing solvent (preferably water, or organic solvent such as an alcohol) from PF. Among preferred solvent for preparing the PF dispersions are water and organic solvents such as alcohols.

The heat treatment is preferably carried out at a temperature ranging from 400 to 2.800° Celsius, and more preferably at a temperature ranging from 1.000 to 2.500° C.

A sixth object of the present invention is constituted by a process for preparing a negative electrode. This process comprises the steps of:

-   -   a) dispersing and mixing, preferably by using ball milling, at         least one Carbon#1 powder, in preferably a liquid Phenolic Resin         (PF), the mixing process being preferably continued until         complete dispersion of carbon#1 in the PF and preferably until         vaporization of 40 to 60 wt % of the containing solvent         (preferably water, or organic solvent such as an alcohol) from         the PF;     -   b) poring the mixture obtained in the preceding step on a         support, preferably on a flat Al-plate, on a Cu-plate, on an         alu-Exmet or on a cupfer Exmet, then heated preferably to         150-175° C., more preferably to 160-170° C. and thermally         soaked, for 1 to 5 hours, preferably for about 2.0 hours, the         heating rate varying preferably from 3-8° C./min depending on         the thickness of the sample;     -   c) after the preceding heating step, preferably converting the         sample into solid sheets from which the support (AL-plate was         separated); and     -   d) treating the Carbon#1: polymerized PF-matrix obtained in the         preceding step at a temperature ranging from 600 to 2.500° C.,         preferably at a temperature ranging from 600 to 1.000° C. using         30-50° C./min heating rate following thermal profile shown in         FIG. 1. Then the carbon#2 is produced by carbonization of         PE-matrix.

Any polymeric material, particularly any polymeric material with a high carbon content and more preferably any PF transforms to graphite up to beating through the following process:

-   -   1. PF Polymerizes to a rubbery gel on heating to 85° C. (gelling         process);     -   2. on heating to 120° C., the rubbery gel cures to form a hard         cross-linked polymer by condensation reaction which produces         water;     -   3. on heating to 225° C., the hard cross-linked polymer obtained         in step 2 forms yellowish transparent material with lower         density that its previous stages, this coincides with loss of         more water and material having high porosity, at this stage         neighboring carbon chains merge and start forming 3D-carbon         matrixes;     -   4. on heating to from 225° C. to 500° C., the material obtained         in the preceding step becomes free of water and yet contains         appreciable amounts of hydrogen, this step is know as         pre-carbonization carbonization step which was critical in         controlling the porosity of the host material. Slower heating         leads to smaller pore sizes;     -   5. on heating to 1000-1250° C., material volume shrinks, its         electrical conductivity increases by many orders of magnitudes;     -   6. at temperatures above 1200° C., the material being depleted         of hydrogen; and     -   7. further cross-linking and carbon chains start growing in 2D &         3D directions, this means that carbon#2 sticks on the surface of         the carbon#1 particles and carbon#2 squeezes into itself when         the temperature is increased to 2500° C.

In the following examples, the PF material used was supplied in the year 2001 by Georgia Pacific Co., Lawrenceville, Ga., in the United States of America under the reference Products # PF211.

Here, we are proposing the application of a new Carbon#1-Carbon#2 composite as N-E material for battery systems consisted of winded/stacked layers of electrodes with potential differences between them being dependant on their electrochemical properties. The other disclosing element of this proposal is the processing of the carbon-carbon composites noted above. The proposed material consists of carbon-carbon composite of 10-100 μm particles.

This consisted of a highly graphitic carbon (e.g. graphite) embedded within or surrounded by the matrix of a second carbon that has a low degree of graphitization known as hard carbons).

The low cristallinity carbon constituting of Carbon#1 has a sloppy voltage and a high medium voltage about 500 mV vs Li⁺/Li. This high sloppy voltage will be affected on the decreasing of the energy density of the batteries. However this is compatible with PC based electrolyte. This type of electrolyte is suitable for low temperature applications.

The high cristallinity carbon constituting of Carbon#2 has a flat voltage and low medium voltage about 100 mV vs Li+/Li. This low flat voltage will be affected on the increasing of the energy density of the batteries. However it is not compatible with PC based electrolyte.

EXAMPLES

The following examples are given for illustrative purpose only and may not be construted as constituing a limitation of the present invention.

Sample Preparation:

The following steps were used to prepare the proposed material:

-   -   1—a Carbon#1 powder was dispersed in Liquid Phenolic Resin (PF)         and the mixed using mixture ball milling. The mixing process was         continued until complete dispersion of Carbon#1 in the PF and         vaporization of 40 -60 wt % of the containing alcohol from PF,         both were assured.     -   2—the item-1 mixture was pored on flat Al-plate, then heated to         150-175° C. and thermally soaked for 2.0 hours. The heating rate         could vary from 3-8° C./min depending on the thickness of the         sample, in our case heating of 5° C./min was used. After this         heating process, the sample converts into solid sheets from         which the AL-plate was separated.     -   3—item-3 (Carbon#1: polymerized PF-matrix) heat treated to         600° C. and then to 1000 or 2500° C. using 30-50° C./min heating         rate following thermal profile shown in FIG. 1.

The PF matrix polymerizes and pre-carbonizes up to 450-475° C. During this step, PF generates water, which vaporizes while beating. This leads to increasing density and decreasing volume. Between 500-600 PF begins the early stages of carbonization steps, where the carbon graphite-sheets start buckling-up and building three-dimensional matrixes of randomly oriented short carbon layers with porous structure. PF porosity could depend on heat rate and thermal-soaking time in this temperature range. For longer heating time between 475-600° C., the PF pores size to become smaller. Above 600° C., the graphitization step starts and the graphite layer cross-link further. This process tends to squeeze the carbon#1 particles closer together and provides carbon-carbon composites with the low graphitized carbon matrix pressing over the highly graphitized carbon particles.

FIG. 3 shows Transmission Electron Microgaph of the carbon-carbon composite heat treated to 2.500° C. and as prepared according to samples 3 and 4.

The following Table 1 lists the data of carbon-carbon composite samples prepared for proof of the concept. TABLE I Pore Area Ave. Bulic Density Skeletal No. Sample Description (m²/g) Dia. (μ) (g/cm3) Density 1 100 g PF 9.184 ± 0.02 0.482 0.584 1.267 50 g-SPG-44 1000° C. 2 100 g PF 13.193 ± 1    0.243 0.605 1.162 40 g-SFG-44/5% LiNO3 1000° C. 3 100 g PF 3.198 ± 0.05 0.123 0.988 1.095 70 g-SFG-44 2500° C. 4 100 g PF 6.550 ± 0.12 0.437 0.532 1.413 70 g-SFG-15 2500° C.

Carbon#1 is a carbon derived by heat treatment from 1.000 to 2.500 Celcius preferably at 1.000 degrees Celcius) from phenolic resin.

Carbon#2 is an artificial graphite—commercialized under the name SFG 44 (particles having a size of 44 micrometers) and under the name SFG 15 (particles having a size of 15 micrometers by the Company Timcal (anciently Lonza in Swiss).

Example 1

In this example the carbon-carbon composite was made by mixing 100 g PF with 50 g of SFG-44 (artificial graphite) commercialized by Timcal (Swiss) and heated at 1.000° C. for 2 hours in argon atmosphere. The SEM image of the carbon-carbon material of the sample 1 is shown in FIG. 1. The carbon#2 is derived from carbonization of PF, which cover partially the surface of carbon#1 (grdphite) The electrochemical performance was obtained by using 1M LiClO₄ in EC-DMC as electrolyte. Three electrodes cell was used with lithium metal as counter electrode and reference. The reversible capacity of sample #1 is 218 mAh/g at C/12 rate (charge and discharge in 12 hours). The coulombic efficiency of the first cycle was 85%.

Example 2

In this example the carbon-carbon composite was made by mixing 100 g PF with 40 g-SFG44/5% LiNO3 and heated at 1000° C. for 2 hours in argon atmosphere. The SEM image of the carbon-carbon material of the sample 2 is shown in FIG. 2. The carbon#2 is derived from carbonization of PF, which cover almost totally of the surface of carbon#1 (graphite). The particle size of carbon#2 is from 39 nm to 500 nm. The electrochemical performance was obtained by using 1M LiClO₄ in EC-DMC as electrolyte. Three electrodes cell was used with lithium metal as counter electrode and reference. The reversible capacity of sample #2 is 259 mAh/g at C/12 rate (charge and discharge in 12 h). The coulombic efficiency of the first cycle was 82%.

Example 3

In this example the carbon-carbon composite was made by mixing 100 g PF with 70 g-SFG-15 and heated at 2500° C. for 1 minute in argon atmosphere. The SEM image of the carbon-carbon material of the sample 3 is shown in FIG. 3. The carbon#2 is derived from carbonization of PF, which cover partially the surface of carbon#1 (graphite), but still some graphite particle not covered at all. The particle size of carbon#2 is from 20 nm to 500 nm.

The electrochemical performance was obtained by using 1M LiClO₄ in EC-DMC as electrolyte. Three electrodes cell was used with lithium metal as counter electrode and reference. The reversible capacity of sample #3 is 235 mAh/g at C/12 rate (charge and discharge in 12 h). The coulombic efficiency of the first cycle was 45%.

Example 4

In this example the carbon-carbon composite was made by mixing 100 g PF with 70 g-SFG-15 and heated at 2500° C. for 2 hours in argon atmosphere. The SEM image of the carbon-carbon material of the sample 3 is shown in FIG. 4. The carbon#2 is derived from carbonization of PF, which covers almost totally the surface of carbon#1 (graphite). The carbon#2 is more compact, it's particle size is from 20 nm to 500 nm.

The electrochemical performance was obtained by using 1M LiClO₄ in EC-DMC as electrolyte. A three electrodes cell was used with lithium metal as counter electrode and reference. The reversible capacity of sample #4 is 280 mAh/g at C/12 rate (charge and discharge in 12 h). The coulombic efficiency of the first cycle was 56%

Among the improved properties of the new carbon-carbon material of the present invention over the known materials and particularly over the known NE materials are inter alia:

-   -   the compatibility with propylene carbonate (PC);     -   the low volume expansion;     -   the high electrode density; and     -   the low reactivity (safety).

It is to be understood that, while the foregoing invention has been described in detail by way of illustration and example, numerous modifications, substitutions, and alterations are possible without departing from the spirit and scope of the invention as described in the following claims. 

1-41. (canceled)
 42. A composite of particles of Carbon#1-Carbon#2, wherein Carbon#1 means a low cristallinity carbon and Carbon#2 means a high cristallinity carbon.
 43. A composite of particles of Carbone#1-Carbon#2 according to claim 42, wherein the Carbon#1 has, as measured by a wide-angle X ray diffraction, a low cristallinity characterized by an average lattice constant d=(002) of 0.350 nm or more and a crystallite size L=(002) in the direction of C axis of 25 nm or less.
 44. A composite of particles according to claim 42, wherein the low cristallinity carbon is selected in the group constituted by glassy carbon, polymer derived carbons and petroleum coke.
 45. A composite of particles according to claim 42, wherein the Carbon#2 has a high crystallinity as measured by a wide-angle X ray diffraction, average lattice constant d=(002) of 0.338 nm or less and a crystallinity size L=(002) in the direction of C axis of 40 nm or more.
 46. A composite of particles according to claim 45, wherein the high cristallinity carbon is selected in the group constituted by graphite, kish graphite, pyrolytic graphite, gas-growth graphite and any artificial graphite.
 47. A composite of particles according to claim 45, wherein the high cristallinity carbon is selected in the group constituted by natural graphites.
 48. A composite of particles of Carbone#1-Carbon#2 according claim 42, wherein the package density of said particles, measured according to the tap density method associated to the apparatus commercialized under the name Logan Instrument Corp. Model Tap-2, is superior or equal to 0,5 g/cc.
 49. A composite of particles of Carbone#1-Carbon#2 according to claim 42, wherein the particle size of said particles, measured according to the SEM method, associated to the apparatus Microtrac model X100 Particle Analyser, ranges from 0.5 to 100 micrometers.
 50. A composite of particles of Carbone#1-Carbon#2 according to claim 42, having according to the BET method, a specific surface area ranging from 1 to 50 m²/g.
 51. A composite of particles according to claim 42, wherein the Carbone#1 is at least partially embedded or surrounded by a matrix of Carbon#2.
 52. A composite of particles according to claim 51, wherein at least 50% of the external surface of the Carbon#1 is embedded or surrounded by a matrix of Carbon#2.
 53. A composite of particles according to claim 51, wherein at least 70% of the external surface of the Carbon#1 is embedded or surrounded by a matrix of Carbon#2.
 54. A composite of particle according to claim 42, wherein the carbon#2 is partially embedded or surrounded by a matrix of Carbon#1.
 55. A composite of particles according to claim 54, wherein at least 50% of the external surface of the Carbon#2 is embedded or surrounded by a matrix of Carbon#1.
 56. A composite of particles according to claim 54, wherein at least 70% of the external surface of the Carbon#2 is embedded or surrounded by a matrix of Carbon#1.
 57. A composite of particles of a high cristallinity carbon embedded within or surrounded by a matrix of a second carbon that has lower degree of cristallinity.
 58. A composite of particles according to claim 57, wherein the high cristallinity carbon is a graphitic carbon.
 59. A composite of particles according to claim 57, wherein the second carbon that has a low degree of cristallinity is a graphitized carbon (also known as a hard carbon).
 60. A composite of particles according to claim 42, having a size measured according to the SEM (Scanning Electron Microscopy) method ranging from 1 to 50 micrometers.
 61. A composite of particles according to claim 42, having a size measured according to the SEM (Scanning Electron Microscopy) method ranging from 12 to 20 micrometers.
 62. A composite of particles of high cristallinity carbon having a particle size ranging from 1 to 50 micrometers, said high cristallinity carbon particles being at least partially covered by particles of low cristallinity having a particle size ranging from 10 to 500 nm, said low cristallinity carbon particles being attached to the surface of said high cristallinity carbon particle.
 63. A composite of particles according to claim 62, wherein the size of the high cristallinity carbon particles ranges from 1 to 50 μm.
 64. A composite of particles according to claim 62, wherein the size of the high cristallinity carbon particles ranges from 5 μm to 20 μm.
 65. A composite of particles of low cristallinity carbon having a particle size ranging from 1 to 50 micrometers, said low cristallinity carbon particles being at least partially covered by particles high cristallinity carbon particles having a particle size ranging from 1 to 50 micrometers, said low cristallinity carbon particles being attached to the surface of said high cristallinity carbon particle.
 66. A composite of particles according to claim 65, wherein the size of the low cristallinity carbon particles ranges from 1 μm to 50 μm.
 67. A composite of particles according to claim 65, wherein the size of the low cristallinity carbon particles ranges from 5 μm to 20 μm.
 68. Use of particles according to claim 42 in electrochemical systems, in sport equipments, in foundry industry, in the car and in aeronautic industries, and as a constituent of electrode material
 69. Use according to claim 68, as constituent of negative electrode (N-E) material.
 70. A negative electrode comprising between 2 to 98 weight per cent of a composite material according to claim
 42. 71. A negative electrode according to claim 70, wherein it comprises from 90 to 98 weight per cent of the composite material.
 72. A negative electrode according to claim 70, wherein it further comprises at least one binder.
 73. A negative electrode according to claim 72, wherein said at least one binder is of the PVDF type.
 74. A battery system comprising at least one electrode containing composite particles according to claim
 42. 75. A battery system according to claim 74, wherein the electrode containing composite particles is a negative electrode.
 76. A battery system according to claim 74, wherein it is of the N-E/electrolyte/PE type.
 77. A battery system according to claim 74, wherein said batteries system consists of wined/stacked layers of electrodes.
 78. Li-ion battery comprising a negative electrode, a positive electrode and a porous polymer membrane separator, wherein at least one of said electrodes is an electrode according to claim
 70. 79. Li-ion battery according to claim 78, wherein the porous polymer membrane separation is of the Celgard type.
 80. A process for preparing the carbon-carbon composite material particles according to claim 42, which process comprising the steps of dispersing and mixing at least one Carbon#1 powder, in a polymeric substance that results in carbon particles by heat treatment.
 81. A process according to claim 80, wherein the heating last from 5 minutes to 12 hours.
 82. A process according to claim 80, wherein the heating is carried out at a temperature ranging from 400° C. to 2800° C.
 83. A process according to claim 80, wherein the heating is carried out at temperature ranging from 1000° C. to 2500° C.
 84. A process according to claim 80, wherein the polymeric substance is dispersed in a solvent.
 85. A process according to claim 80, wherein the dispersing step is carried out by using ball milling.
 86. A process according to claim 80, wherein the polymeric substance is a liquid Phenolic Resin (PF).
 87. A process according to claim 80, wherein the mixing process is continued until complete dispersion of Carbon#1 in the polymeric substance.
 88. A process according to claim 80, wherein the mixing process is continued until vaporization of 40 to 60 wt % of the containing solvent from the polymeric substance.
 89. A process according to claim 80, wherein the solvent is selected in the group constituted by water and organic solvents.
 90. A process according to claim 89, wherein the organic solvent is an alcohol.
 91. A process for preparing a negative electrode according to claim 70 comprising the steps; a) dispersing and mixing, at least one Carbon#1 powder, with a polymeric material that may be converted in carbon particles by heat treatment; b) putting the mixture obtained in the preceding step on a support, then heating said support covered by said mixture; c) after the preceding heating step, alternatively converting the sample obtained into solid sheets from which the support is separated; and d) treating the Carbon#1: polymerized polymeric material-matrix formed in the preceding steps b) or c) on the support, by temperature.
 92. A process according to claim 91, wherein in step b) the support covered by said mixture is thermally soaked.
 93. A process according to claim 91, wherein in step a) dispersing and mixing are carried out by ball milling.
 94. A process according to claim 91, wherein in step a) the polymeric material is a polymeric material with a high carbon content.
 95. A process according to claim 91, wherein in step a) the polymeric material is selected in the group constituted by liquid Phenolic Resins (PF), solubilized polysaccharides and mixture thereof.
 96. A process according to claim 94, wherein in step a) the dispersion of carbon#1 is continued until vaporization of 40% to 60% of the solvent used to liquefying or for solubilizing the polysaccharide.
 97. A process according to claim 91, wherein in step b) the support is heated to 150 to 175° C.
 98. A process according to claim 91, wherein in step b), the support is heated to 160° C. to 170° C.
 99. A process according to claim 92, wherein in step b), the support is soaked for 1 to 5 hours.
 100. A process according to claim 92, wherein in step b), the support is soaked for about two hours.
 101. A process according to claim 91, wherein the heating rate varies from 3 to 8° Celcius by minute, depending on the thickness of the sample.
 102. A process according to claim 91, wherein in step d) the temperature ranges from 400 to 2.800° C.
 103. A process according to claim 91, wherein in step d) the temperature ranges from 600 to 2.500° C.
 104. A process according to claim 102, wherein the heating is carried out at a rate, ranging from 30 to 50° C./min.
 105. A process according to claim 102, wherein the heating is carried out at a rate that follows the thermal profile shown in FIG.
 1. 106. A process according to claim 95, wherein the liquid Phenolic Resin is selected in the group consisting of novolacs, resoles and polybenzylic ethers.
 107. A process according to claim 96, wherein the polysaccharide is selected in the group constituted by gelatinized starches.
 108. A process according to claim 106, wherein the liquid Phenolic Resin or the gelatinized starch is in the form of a slurry that presents a good applicability and a good adhesion on the support constituted by carbon#1 particles. 